Phosphonium salts and processes for production of and uses for the same

ABSTRACT

Novel phosphonium salts of the general formula ##STR1## wherein R 1  and R 2  each is a hydrogen atom or a hydrocarbon group of 1 to 12 carbon atoms which may optionally be substituted; R 3  is a hydrogen atom or a hydrocarbon group of 1 to 5 carbon atoms which may optionally be substituted; R 4 , R 5  and R 6  each is a hydrocarbon group of 1 to 8 carbon atoms which may optionally be substituted; X is a hydroxyl group, a hydroxycarbonyloxy group or a lower alkylcarbonyloxy group, and processes for production of the salts are described. Telomerization catalysts containing said phosphonium salts and processes for production of straight-chain alkadienyl compounds using the same catalysts are also provided.

This is a division of patent application Ser. No. 07/211,034, filed onJune 24, 1988, now U.S. Pat. No. 4,927,910.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel phosphonium salts and processesfor production of and uses for the same.

2. Description of the Related Art

of Chemical Research, 6, 8-15 (1973) and R. F. Heck, "Palladium Reagentsin Organic Syntheses", pp.325-334, Academic Press, New York, 1985describe that 1-substituted-2,7-alkadienes can be synthesized bysubjecting a conjugated diene, such as butadiene, isoprene, etc., totelomerization reaction with an active hydrogen compound, such as water,alcohols, carboxylic acids, amines, ammonia, enamines, active methylenecompounds, azides, silanes, etc., in the presence of a palladiumcatalyst and that favorable results can be obtained in the concomitantpresence of a ligand such as triphenylphosphine in the reaction system.##STR2## wherein R is a hydrogen atom or a methyl group; and Y is agroup derived from an active hydrogen compound by removal of one activehydrogen atom.

As an example of the production of a 1-substituted-2,7-alkadienecompound by such telomerization reaction, there may be mentioned theproduction of 2,7-octadien-1-ol by telomerization reaction of butadienewith water as described in U.S. Pat. Nos. 3,670,032, 3,992,456,4,142,060, 4,356,333 and 4,417,079, for instance.

It is generally acknowledged that in the telomerization reaction of aconjugated diene with an active hydrogen compound in the presence of apalladium catalyst, the use of a tertiary phosphorus compound, such astri-substituted phosphines or tri-substituted phosphites, as a ligand isnot only useful for modulating the reaction rate and reactionselectivity but also instrumental in stabilizing the catalyst.Therefore, as the catalyst for a telomerization reaction, it is commonpractice to use a low-valence palladium complex containing a ligand,such as a tri-substituted phosphine, or a chemical species prepared byreducing a palladium (II) compound in the presence of a ligand such as atri-substituted phosphine. However, the following problems are involvedin telomerization reactions using such catalysts.

(1) The higher the concentration of the ligand, such as a phosphinecompound, or the higher the molar ratio of the ligand to palladium, thehigher is the stability of the palladium catalyst but the reaction rateis conversely decreased drastically (Chemical Communications, 1971, 330;etc.) and the higher the molar ratio of ligand to palladium, the loweris the selectivity of the reaction to a straight-chain alkadienylcompound, i.e. a compound derived by substitution of one or more activehydrogen atoms of an active hydrogen compound by 2,7-alkadienyl groups(Chemical Communications, 1971, 330; U.S. Pat. No. 3,992,456; etc.).Therefore, it is difficult to reconcile the requirements imposed bythese two conflicting tendencies, i.e. stabilization of the palladiumcatalyst on the one hand and enhancement of high reaction rate and highselectivity to a straight-chain alkadienyl compound on the other hand.

(2) The phosphine compound used as a ligand is liable to be oxidized inthe presence of palladium [Angewandte chemie international Edition inEnglish, 6 92-93 (1967)] and as the phosphine compound is recycled fortelomerization reaction over a long time, there occurs an accumulationof its oxidation product, i.e. the phosphine oxide, but this phosphineoxide acts as a catalyst poison to exert adverse effects ontelomerization (Japanese Patent Application Laid-Open KOKAI No.4103/76). Incidentally, the phosphine oxide is hard to be separated andremoved.

(3) The research of the present inventors revealed that when atelomerization reaction is carried out using an excess of a phosphinecompound relative to palladium, even if a low-valence palladium complexprepared from a palladium compound and a phosphine compound, theso-called active catalyst species, is used, the reaction involves aprolonged induction time. Particularly where the telomerization reactionis continuously conducted over a long period of time, more than anecessary amount of the palladium catalyst must be added, for the addedcatalyst cannot immediately exhibit its activity.

Since palladium is an expensive noble metal, it must be ensured in theuse of a palladium catalyst in commercial production that theproductivity per unit quantity of palladium be sufficiently high and thecatalytic activity be sustained over a long time. From this point ofview, it is of utmost importance to solve the aforesaid problems (1) to(3).

SUMMARY OF THE INVENTION

It is an object of the invention to provide a novel phosphonium saltwhich is of value as a component of the highly active catalyst fortelomerization reaction.

It is another object of the invention to provide a process for producingsaid phosphonium salt.

It is a further object of the invention to provide a telomerizationcatalyst containing said phosphonium salt which has high activity.

It is still another object of the invention to provide a process forproducing straight-chain alkadienyl compounds using said telomerizationcatalyst.

The present invention, in one aspect thereof, provides a phosphoniumsalt of the general formula ##STR3## wherein R¹ and R² each is ahydrogen atom or a hydrocarbon group of 1 to 12 carbon atoms which mayoptionally be substituted; R³ is a hydrogen atom or a hydrocarbon groupof 1 to 5 carbon atoms which may optionally be substituted; R⁴, R⁵ andR⁶ each is a hydrocarbon group of 1 to 8 carbon atoms which mayoptionally be substituted; X is a hydroxyl group, a hydroxycarbonyloxygroup or a lower alkylcarbonyloxy group.

The present invention in another aspect provides a process for producinga phosphonium salt of general formula (I) characterized by reacting atri-substituted phosphine of the general formula ##STR4## wherein R⁴, R⁵and R⁶ have the meanings defined hereinbefore, with at least one molarequivalent, relative to said tri-substituted phosphine, of an allyliccompound of the general formula ##STR5## wherein R¹, R² and R³ have themeanings defined hereinbefore; R⁷ is a hydrogen atom or a loweralkylcarbonyl group, in the presence of a palladium compound in thepresence or absence of water containing carbonate and/or hydrogencarbonate ion.

In a third aspect, the present invention provides a telomerizationcatalyst characterized by comprising a phosphonium salt of generalformula (I) and a palladium compound.

In a fourth aspect, the present invention provides a process forproducing a straight-chain alkadienyl compound which comprises reactinga conjugated diene with an active hydrogen compound in the presence ofsaid telomerization catalyst.

DETAILED DESCRIPTION OF THE INVENTION

Referring to the above general formula (I), R¹, R², R³, R⁴, R⁵, R⁶ and Xare further explained in detail below. The hydrocarbon group of 1 to 12carbon atoms, independently represented by R¹ and R², is exemplified byaliphatic hydrocarbon groups such as alkyl groups, e.g. methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-octyl, etc., and alkenyl groups, e.g.2-propenyl, 3-butenyl, 4-pentenyl, etc.; alicyclic hydrocarbon groupssuch as cycloalkyl groups, e.g. cyclohexyl etc.; and aromatichydrocarbon groups such as aryl groups, e.g. phenyl, tolyl, etc., andaralkyl groups e.g. benzyl and so on. The hydrocarbon group of 1 to 5carbon atoms, represented by R³, is exemplified by aliphatic hydrocarbongroups such as alkyl groups, e.g. methyl, ethyl, propyl, etc., andalkenyl groups, e.g. allyl, 4-pentenyl and so on. The hydrocarbon groupof 1 to 8 carbon atoms, independently represented by R⁴, R⁵ and R⁶, isexemplified by aliphatic hydrocarbon groups such as alkyl groups, e.g.methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-octyl,etc.; alicyclic hydrocarbon groups such as cycloalkyl groups, e.g.cyclohexyl, methylcyclohexyl, etc.; and aromatic hydrocarbon groups suchas aryl groups, e.g. phenyl, tolyl, etc., and aralkyl groups, e.g.benzyl and so on. The substituents which may be present on thehydrocarbon group represented independently by R¹, R², R³, R⁴, R⁵ and R⁶include, among others, di(lower alkyl)amino groups such as dimethylaminoetc.; a cyano group; and groups of the formula --SO₃ M or --COOM (whereM is an alkali metal atom such as lithium, sodium, potassium, etc.). Foruse of the phosphonium salt of general formula (I) as a component of thecatalyst for telomerization reaction, it is preferable in view oftelomerization reaction data that at least one of R⁴, R⁵ and R⁶ is anaryl group which is not substituted, such as phenyl, tolyl or the like,or an aryl group substituted by di(lower alkyl)amino, --SO₃ M or --COOM(where M has the meaning defined hereinbefore), such as ##STR6## or thelike. The lower alkylcarbonyloxy group represented by X is exemplifiedby acetoxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy and soon.

The process for production of phosphonium salts of general formula (I)is described below.

The tri-substituted phosphine of general formula (II), which is used inthe production of a phosphonium salt of general formula (I), isexemplified by aliphatic phosphines such as triisopropylphosphine,tri-n-butylphosphine, tri-t-butylphosphine, tri-n-octylphosphine, etc.;alicyclic phosphines such as tricyclohexylphosphine etc.; and aromaticphosphines such as triphenylphosphine, tritolylphosphine,diphenylisopropyl phosphine, (C₆ H₅)₂ PCH₂ CH₂ SO₃ Na, (C₆ H₅)₂ PCH₂CH(CH₃)COONa, ##STR7## (C₆ H₅)₂ PCH₂ CH₂ N(CH₃)₂, (C₆ H₅)₂ PCH₂ COONaand so on. The lower alkylcarbonyl group, represented by R⁷ in generalformula (III), is exemplified by acetyl, propionyl, butyryl, isobutyryl,valeryl and so on. The allylic compound of general formula (III) isexemplified by allylic alcohols such as allyl alcohol,2-methyl-2-propen-1-ol, 2-buten-1-ol, 2,5-hexadien-1-ol,2,7-octadien-1-ol, 1,4-pentadien-3-ol, 1,7-octadien-3-ol, 2-octen-1-ol,etc.; and esters of such allylic alcohols with a carboxylic acid of thegeneral formula

    R.sup.8 OH                                                 (IV)

wherein R⁸ is a lower alkylcarbonyl group, such as allyl acetate,2-methyl-2-propenyl acetate, 2,5-hexadienyl acetate, 2,7-octadienylacetate, 1-vinyl-5-hexenyl acetate, 1-vinyl-2-propenyl propionate,2-octenyl propionate and so on. The amount of such allylic compound tobe used in the production of a phosphonium salt of general formula (I)is not less than equimolar with respect to the tri-substitutedphosphine. There is no critical upper limit to the amount of the allyliccompound but in consideration of the ease of removal of the excessallylic compound after formation of the phosphonium salt of generalformula (I), the allylic compound is preferably used in a proportion ofabout 1 to 10 moles per mole of the tri-substituted phosphine.

The palladium compound to be present in the reaction system for theproduction of a phosphonium salt of general formula (I) may be selectedfrom among those palladium compounds which can be used generally fortelomerization of conjugated dienes. As specific examples, there may bementioned palladium (II) compounds such as palladium acetylacetonate,π-allyl-palladium acetate, palladium acetate, palladium carbonate,palladium chloride, bisbenzonitrilepalladium chloride, etc. andpalladium (O) compounds such as bis(1,5-cyclooctadiene)palladium,tris(dibenzylideneacetone)dipalladium and so on. Where a palladium (II)compound is used, there may be added a reducing agent for reduction ofpalladium (II) to palladium (O). The reducing agent used for thispurpose is exemplified by alkali metal hydroxides such as sodiumhydroxide etc., formic acid, sodium phenolate, NaBH₄, hydrazine, zincpowder, magnesium and so on. The preferred amount of the reducing agentmay generally range from the stoichiometric amount required forreduction to about 10 times the amount. The amount of the palladiumcompound is such that there be made available 0.1 to 10 milligram-atoms,preferably 0.5 to 5 milligram-atoms of palladium per litter of thereaction mixture.

The reaction for the formation of a phosphonium salt of general formula(I) is carried out in the presence of the palladium compound and in thepresence or absence of water containing carbonate ion and/or hydrogencarbonate ion. Where an allylic alcohol is used as the allylic compound,the reaction is generally conducted in the presence of water containingcarbonate ion and/or hydrogen carbonate ion, whereby a phosphonium saltof general formula (I) wherein X is a hydroxyl group or ahydroxycarbonyloxy group is formed. When the ester of an allylic alcoholwith a carboxylic acid of general formula (IV) is used as the allyliccompound, the reaction can be conducted in the absence of said watercontaining carbonate ion and/or hydrogen carbonate ion, whereby aphosphonium salt of general formula (I) wherein X is a loweralkylcarbonyloxy group is produced. It is practically preferred thatsaid carbonate ion and/or hydrogen carbonate ion be derived from carbondioxide, a hydrogen carbonate such as sodium hydrogen carbonate, or acarbonate such as sodium carbonate within the reaction system. Amongthem, the ion derived from carbon dioxide is particularly desirable.Where carbon dioxide is used, a tertiary amine or quarternary ammoniumhydroxide may be added for the purpose of increasing the carbonate ionconcentration in the reaction system. The carbon dioxide partialpressure, where carbon dioxide is used, may range generally from 0 to 50atmospheres (gage pressure) and, for practical purposes, is preferablyin the range of 0 to 10 atmospheres (gage pressure).

The reaction for the formation of a phosphonium salt of general formula(I) may be conducted in the presence of an organic solvent which isinert to the reaction and is capable of dissolving the tri-substitutedphosphine of general formula (II) and the allylic compound of generalformula (III). Examples of such organic solvent include various etherssuch as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane,dioxolane, ethylene glycol dimethyl ether, polyethylene glycol dimethylether with an average molecular weight of 200 to 2,000, etc.; secondaryor tertiary alcohols such as t-butanol, isopropyl alcohol, etc.; ketonessuch as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.;nitriles such as acetonitrile, benzonitrile, propionitrile, etc.; amidessuch as acetamide, propionamide, N,N-dimethylformamide,N,N-dimethylacetamide, etc.; sulfoxides such as dimethyl sulfoxide etc.;sulfones such as sulfolane, methylsulfolane, etc.; phosphoric acidamides such as hexamethylphosphoramide etc.; esters such as methylacetate, ethyl acetate, methyl benzoate, ethylene carbonate, etc.;aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene,etc.; and cyclic or acyclic aliphatic hydrocarbons such as butene,butane, hexane, cyclohexane, methylcyclohexane and so on. These solventsare generally used singly but may be used in combination as well.

The reaction for the formation of a phosphonium salt of general formula(I) is generally carried out at a temperature of 10° C. to 80° C. and,for practical purposes, preferably at room temperature. The reaction isgenerally carried through in 0.5 to 24 hours, and the end-point ofreaction can be easily ascertained by such a procedure as ³¹ P-nuclearmagnetic resonance spectrometry, liquid chromatography, iodometry or thelike. As the atmosphere for the reaction, gases that do not adverselyaffect the reaction, such as carbon dioxide gas, nitrogen gas, etc., canbe advantageously employed either singly or as a mixture.

The separation and purification of the phosphonium salt of generalformula (I) from the resulting reaction mixture can be carried out bythe following or other procedures. From the reaction mixture, theunreacted allylic compound and water, etc. are first distilled off underreduced pressure as necessary and the residue is washed with a solvent,such as methanol, diethyl ether, etc., to obtain crystals of thephosphonium salt of general formula (I).

The phosphonium salt of general formula (I), when used in combinationwith a palladium compound, gives a catalyst for use in thetelomerization reaction of a conjugated diene with an active hydrogencompound. The amount of the phosphonium salt of general formula (I) as acomponent of this telomerization catalyst is generally at least 6 molesper gram-atom of palladium in the palladium compound, preferably 10 to200 moles on the same basis, and for still better results, 30 to 100moles on the same basis. The palladium compound as a component of saidtelomerization catalyst is any of the palladium (O) compounds orpalladium (II) compounds which can be used in the reaction for theformation of a phosphonium salt of general formula (I). Where apalladium (II) compound is employed, the telomerization reaction can beconducted in the additional presence of a reducing agent. This reducingagent may be the same reducing agent as mentioned hereinbefore inconnection with the reaction for the preparation of a phosphonium saltof general formula (I). The amount of the reducing agent is preferablyin the range from the stoichiometric amount required for reduction to 10times that amount. The telomerization catalyst comprising a phosphoniumsalt of general formula (I) and a palladium compound can be added to thetelomerization reaction system by the following alternative procedures.Thus, the phosphonium salt and the palladium compound may beindependently added or a mixture of the phosphonium salt and palladiumcompound may be added to the reaction system. An example of the lattermethod of addition is that the reaction mixture containing thephosphonium salt and palladium compound as obtained by the reaction forthe formation of the phosphonium salt of general formula (I) is fed,either directly or after an appropriate workup procedure such asconcentration or dilution, to the telomerization reaction system. Theamount of the telomerization catalyst is such that the concentration ofthe palladium compound as a component of the catalyst is 0.1 to 10milligram-atoms of palladium per liter of the telomerization reactionmixture and preferably 0.5 to 5 milligram-atoms on the same basis.

The conjugated diene to be used as a starting material in thetelomerization reaction which is conducted with the aid of the abovetelomerization catalyst comprising a phosphonium salt of general formula(I) and a palladium compound may for example be butadine, isoprene orthe like. The active hydrogen compound to be reacted with such aconjugated diene is a compound containing at least one reactive hydrogenatom, such as alcohols, phenols, amines, carboxylic acids, water,silanes, and active methyl, methylene or methine compounds activated bycarbonyl, cyano, nitro, or the like. Among said alcohols are methanol,ethanol, butanol, allyl alcohol, 2-ethylhexanol, octadienol, stearylalcohol, diethylene glycol, neopentyl glycol, pentaerythritol,trimethylolpropane, polyethylene glycol and so on. Among said phenolsare phenol, cresol and so on. Said amines include ammonia, methylamine,dimethylamine, ethylamine, diethylamine, butylamine, morpholine,piperazine and so on. Among said carboxylic acids are acetic acid,propionic acid, adipic acid, benzoic acid, phthalic acid and so on. Thesilanes mentioned above are dimethylsilane, diethylsilane,dimethoxysilane and so on. Among said active methyl, methylene ormethine compounds are methyl acetoacetate, acetylacetone, nitromethane,methyl cyanoacetate, ethyl 2-formyl-2-phenylacetate,2-methyl-3-oxobutanenitrile, and so on.

In conducting the telomerization reaction, an additive may be used toincrease the reaction rate. Examples of said additive include variousbases such as alkali metal hydroxides, aliphatic tertiary amines, etc.,salts of such bases with an acid which may for example be carbonic acid,phosphoric acid, acetic acid, boric acid or methanesulfonic acid, andweak acids such as boric acid, phosphorous acid, phenol and so on. Amongthese additives, one that is suited to the species of starting compoundand other conditions is selectively used. For example, an increasedreactivity of the active hydrogen compound can be expected by using analiphatic tertiary amine as said additive when the active hydrogencompound is a carboxylic acid or by using the carbonate or hydrogencarbonate of an aliphatic tertiary amine when water is used as theactive hydrogen compound.

The telomerization reaction can be conducted with the active hydrogencompound being utilized as a solvent as well but may likewise beconducted in the presence of an independent organic solvent that doesnot interfere with the reaction. As examples of such organic solvent,there may be mentioned those organic solvents which can, as aforesaid,be present in the reaction system for the formation of the phosphoniumsalt of general formula (I).

The telomerization reaction is carried out generally at a temperature of40° C. to 100° C. and preferably in the range of 60° C. to 80° C. Whilesuch telomerization reaction can be conducted batchwise or continuously,a continuous process is preferable for commercial purposes.

By the telomerization reaction using the telomerization catalystcomprising a phosphonium salt of general formula (I) and a palladiumcompound, a straight-chain alkadienyl compound derived by substitutionof one or more active hydrogen atoms of the active hydrogen compound byone or more 2,7-alkadienyl groups can be produced with high selectivity.The reaction product straight-chain alkadienyl compound can be separatedfrom the catalyst component by a distillation process, for example usinga film evaporator, or an extraction process such as the processesdescribed in U.S. Pat. Nos. 4,356,333 and 4,417,079 but an extractionprocess is preferred in view of lower chances of deactivation of thecatalyst component which make for recycling over an extended time. Thus,for example, where the telomerization reaction is carried out usingwater as the active hydrogen compound and a telomerization catalyst ofthis invention whose phosphonium salt component is a hydrophilicphosphonium salt containing a di(lower alkyl)amino group or a group ofthe formula --SO₃ M or --COOM (where M has the meaning definedhereinbefore) in an organic solvent having a high dielectric constant,such as sulfolane, ethylene carbonate, N,N-dimethylformamide or thelike, extraction of the reaction mixture with a hydrocarbon such ashexane or the like gives the product compound in the extract and thecatalyst component in the extraction residue.

The straight-chain alkadienyl compound thus obtained is useful as asynthetic intermediate for the production of n-octanol, n-octylamine,di-n-octyl phthalate, etc. or as a starting material for the manufactureof polymer modifying agents, perfumes, agricultural chemicals, drugs andso on.

According to the telomerization reaction using a telomerization catalystcomprising a phosphonium salt of general formula (I) and a palladiumcompound, not only is the straight-chain alkadienyl compound can beobtained with high selectivity but the reaction can be conductedsubstantially without an induction time and without formation of theoxidation product of the phosphine compound used which is known to be acatalyst poison. Furthermore, since this catalyst exhibits highactivity, a sufficiently high reaction rate can be achieved even if thephosphonium salt of general formula (I) is used in large excess relativeto the palladium compound for the purpose of improving the stability ofthe catalyst.

A further understanding of this invention can be obtained by referenceto specific examples which are provided hereinbelow for purposes ofillustration only and are not intended to be limitative of thisinvention.

EXAMPLE 1 (Synthesis of a phosphonium salt)

An autoclave equipped with a stirrer and carbon dioxide inlet andpurging lines was charged with 30 ml of ion exchanged water, 110 ml ofdioxane, 0.1 g of palladium acetate, 35 g of lithiumdiphenylphosphino-benzene-m-sulfonate and 25 g of 2,7-octadien-1-ol, andafter the atmosphere in the autoclave was sufficiently purged withcarbon dioxide gas, carbon dioxide gas was further introduced toestablish a pressure of 5 kg/cm² (gage pressure). The temperature of thereaction mixture was increased to 60° C., at which temperature thereaction was conducted for about 20 hours. After completion of thereaction, the solvent was distilled off under reduced pressure and thesolid residue was washed with 100 ml of ether and dried in vacuo at roomtemperature to recover 35 g of white powder.

Analysis of this white powder by high performance liquid chromatography[eluent: 0.01 mole/l aqueous phosphoric acid solution/methanol=1/4;column: YMC-Pack AM312 ODS (Yamamura chemical Lab. Co., Ltd.)] showed nopeak at the position of the starting material phosphine compound and asingle peak at a different position. Based on results of elementalanalysis for C and H and results of colorimetry for P, S and Li, theempirical formula of this compound was determined as C₂₇ H₂₈ O₆ SPLi. Tothe white powder obtained above was added diluted (1N) sulfuric acid andthe carbon dioxide gas evolved thereupon was quantitated by the bariumhydroxide method. As a result, the molar ratio of atomic phosphoruscontained in the white powder to the liberated carbon dioxide gas wasfound to be 1:1. Furthermore, using the above white powder, ¹ H- and ³¹P-NMR spectrometry and IR (infrared) absorption spectrometry werecarried out. Based on results of these determinations, the white powderobtained as above was established to be a compound having the followingstructural formula. ##STR8##

The ¹ H-NMR, IR and ³¹ P-NMR spectrometric data on the product compoundare shown below.

¹ H-NMR spectrum (in CDCl₃, HMDS standard, 90 MHz, ppm) δ: 1.00-1.33 (m,2H), 1.63-2.10 (m, 2H), 4.06 (d of d, J=15 and 6.9 Hz, 2H), 4.66-6.00(m, 5H), 7.3l-7.96 (m, 12H), 7.96-8.40 (m, 2H).

IR spectrum (KBr disk, cm⁻¹) 690, 725, 755, 800, 970, 1040, 1110, 1210,1230, 1400, 1440, 1485, 2940, 3410.

³¹ P-NMR spectrum (in 95% sulfolane-water (w/w), H₃ PO₄ standard, ppm)δ: 21.55.

EXAMPLE 2 (Synthesis of a phosphonium salt)

An autoclave equipped with a stirrer, carbon dioxide inlet, samplingport, feeding port and purging line was charged with 100 g of 85% (byweight) tetra-hydrofuran-water, 50 mg of palladium acetate and 3.16 g oftriphenylphosphine and the mixture was stirred at a carbon dioxidepressure of 5 kg/cm² (gage pressure) for 30 minutes. Then, 3.5 g ofallyl alcohol was fed and the reaction was conducted at an elevatedtemperature of 60° C. for 4 hours. After completion of the reaction, thesolvent was distilled off under reduced pressure to obtain a solidresidue. This solid was washed with 100 ml of ether and dried in vacuoto recover 2.9 g of white powder. Analysis of this powder by highperformance liquid chromatography under the same operating conditions asin Example 1 showed no peak of triphenylphosphine but a single peak at adifferent position. Based on results of elemental analysis, colorimetry,quantitation of carbon dioxide gas, and ¹ H- and ³¹ P-NMR spectrometricdeterminations, the above white powder was identified to be a compoundhaving the following structural formula

    (C.sub.6 H.sub.5).sub.3.sup.61 P--CH.sub.2 CH═CH.sub.2 ·HCO.sub.3.sup.⊖

The ¹ H-NMR data on this compound are shown below.

¹ H-NMR spectrum (in DMSO-d₆, HMDS standard, 90 MHz, ppm) δ: 4.54 (d ofd, J=15.6 and 6.6 Hz, 2H), 5.13-6.03 (m, 3H), 7.53-8.03 (m, 15H).

EXAMPLE 3 (Synthesis of a phosphonium salt)

The reaction and workup procedures of Example 1 were repeated exceptthat 26 g of triphenylphosphine was used in lieu of 35 g of lithiumdiphenylphosphino-benzene-m-sulfonate to give 27 g of white powder.Analysis by high performance liquid chromatography revealed that it wasa single compound different from triphenylphosphine. Furthermore, basedon results of elemental analysis, colorimetry, quantitation of carbondioxide gas, and ¹ H- and ³¹ P-NMR spectrometric determinations, thestructural formula of this compound was established as follows.

    (C.sub.6 H.sub.5).sub.3.sup.61 P--CH.sub.2 CH═CHCH.sub.2 CH.sub.2 CH.sub.2 CH═CH.sub.2. HCO.sub.3.sup.63

The ¹ H-NMR data on this compound are as follows. ¹ H-NMR spectrum(CDCl₃, HMDS standard, 90 MHz, cm⁻¹) δ: 1.05-1.48 (m, 2H), 1.63 -2.08(m, 4H), 4.05 (d of d, J=15 and 6 Hz, 2H). 4.63 -5.91 (m, 5H), 7.32-7.93 (m, 15H),

EXAMPLE 4 (Synthesis of a phosphonium salt)

The reaction and workup procedures of Example 1 were repeated exceptthat 40 g of sodium diphenylphos-phinobenzene-m-sulfonate and 14 g of2-buten-1-ol were used in lieu of 35 g of lithiumdiphenylphosphinobenzene-m-sulfonate and 25 g of 2,7-octadien-1-ol,respectively, to give 33 g of white powder. Analysis by high performanceliquid chromatography revealed that this powder was a single compounddifferent from the starting material phosphine compound. Furthermore,based on results of elemental analysis, colorimetry, quantitation ofcarbon dioxide gas, and ¹ H- and ³¹ P-NMR spectrometric determinations,the structural formula of this product was determined as follows.##STR9##

The ¹ H-NMR data on this product compound are shown below.

¹ H-NMR spectrum (in DMSO-d₆, HMDS standard, 90 MHz, ppm) δ: 1.40-1.65(m, 3H), 4.38 (d of d, J=15.9 and 6.9 Hz, 2H), 5.00 -5.93 (m, 2H), 7.47-8.10 (m, 14H).

EXAMPLE 5 (Synthesis of a phosphonium salt)

A three-necked flask fitted with a magnetic stirrer, carbon dioxideinlet and purging line was charged with 14 g of ion exchanged water and,then, carbon dioxide gas was bubbled into the water. Then, in the carbondioxide gas atmosphere, 6.7 mg of palladium acetate and 0.42 g oflithium diphenylphosphinobenzene-m-sulfonate were fed to the flask. Themixture was stirred for about 30 minutes and 0.55 g of allyl alcohol wasadded using an injection syringe. While carbon dioxide gas was bubbledat atmospheric pressure and room temperature, the stirring was continuedfor about 4 hours. As a result, the reaction goes to completion, givingrise to a white precipitate. The precipitate was filtered through aglass filter and dried in vacuo to recover 0.40 g of white powder.

Analysis of this white powder by high performance liquid chromatography[eluent: 0.01 mole/l aqueous phosphoric acid solution/methanol=1/4, flowrate: 1.2 ml/min; column: YMC-Pack am312 ODS (Yamamura Chemical Lab.Co., Ltd.)] showed no peak at the position of the starting materiallithium diphenylphosphinobenzene-m-sulfonate but a single peak at adifferent position. Furthermore, based on results of elemental analysis,colorimetry, quantitation of carbon dioxide gas, and IR absorption and ¹H- and ³¹ P-NMR spectrometric determinations, the structural formula ofthe above product was determined as follows. ##STR10##

The ¹ H-NMR, IR and ³¹ P-NMR data on the above product compound aregiven below.

¹ H-NMR (DMSO-d₆, HMDS standard, 90 MHz, ppm) δ:4.58 (d of d, J=16.5 and7.1 Hz, 2H), 5.14 -6.00 (m, 3H), 7.57 -8.16 (m, 14H).

IR absorption spectrum (KBr-disk, cm⁻¹) 690, 720, 760, 950, 1000, 1040,1110, 1200 1240, 2940, 3430.

³¹ P-NMR spectrum (95% w/w sulfolane-water, H₃ PO₄ standard, ppm)δ:21.35.

EXAMPLE 6 (Synthesis of a phosphonium salt)

A 300-ml three-necked flask fitted with a stirrer, cooling-condenser andthermometer was charged with 6.9 mg (0.031 mmole) of palladium acetate,4.66 g (0.013 mole) of lithium diphenylphosphinobenzene-m-sulfonate, 3.5g (0.021 mole) of 1-acetoxy-2,7-octadiene and 137 g of acetic acid in anitrogen gas atmosphere and the mixture was refluxed for 4 hours. Aftercompletion of the reaction, the acetic acid was distilled off underreduced pressure using evaporator and the solid residue was washed withether and dried to recover 7.15 g of powder. Analysis by highperformance liquid chromatography revealed that this powder was a singlecompound different from the starting material phosphine compound.Furthermore, based on results of elemental analysis, colorimetry, and IRabsorption spectrometric and ¹ H- and ³¹ P-NMR spectrometricdeterminations, the structural formula of this product compound wasdetermined to be as follows. ##STR11##

The ³¹ P-NMR, ¹ H-NMR and IR data on the product compound are givenbelow.

³¹ P-NMR spectrum (95% sulfolane-water, w/w) 21 ppm

¹ H-NMR spectrum (CDCl₃ /HMDS) δ: 1.06 -1.40 (2H), 1.60-2.20 (4H),1.95(s, 3H), 4.09(d of d, J=15.2 and 7.2 Hz, 2H), 4.66-5.93 (m, 5H),7.46-7.83 (m, 2H), 8 08-8.37 (m, 2H).

IR spectrum (KBr-disk, cm³¹ 1) 665, 690, 720 (cis-olefin), 750, 800, 995(trans-olefin), 1030, 1100, 1200 (--SO₃ Li), 1400, 1570, 1710(OAc.sup.⊖), 2850, 3010

EXAMPLE 7

A 300-ml stainless steel autoclave equipped with an electromagneticstirrer, carbon dioxide inlet, sampling port, feeding port, purging lineand temperature controller was charged with 0.31 g (0.3 mmole) oftris(dibenzylideneacetone)palladium, 6.2 g (12 mmole) of a phosphoniumsalt of the formula ##STR12## N₂ -purged sulfolane, 68 g of water and16.5 g of triethylamine in a nitrogen gas atmosphere. The reactionsystem was purged with carbon dioxide gas and the mixture was stirred ata carbon dioxide pressure of 5 kg/cm² (gage pressure) for 30 minutes.While the carbon dioxide partial pressure of the reaction system wasmaintained at 5 kg/cm² (gage pressure), the internal temperature of thesystem was increased to 75° C. and 40 ml of butadiene was fed in asingle dose to initiate the reaction. After commencement of thereaction, a small amount of the reaction mixture was sampled atpredetermined intervals and analyzed by gas chromatography. As a result,it was confirmed that the telomerization reaction proceeded withoutinvolving an induction period. Results of the analysis are set forth inTable 1.

                  TABLE 1                                                         ______________________________________                                                    Reaction time (hrs)                                                           1    1.5       2       3                                          ______________________________________                                        2,7-Octadien-1-ol                                                                           65.3   124.0     143.0 167.0                                    (mmoles)                                                                      1,7-Octadien-3-ol                                                                           3.3    6.8       7.5   8.9                                      (mmoles)                                                                      Total (mmoles)                                                                              68.6   130.8     150.5 175.9                                    ______________________________________                                    

Analysis of the catalyst solution after 3 hours of reaction revealed noformation of phosphine oxide and also showed that the palladium catalystremained uniformly dissolved without precipitation of palladium metal.

EXAMPLE 8

The reaction procedure of Example 7 was repeated except that 4.37 g (12mmoles) of a phosphonium salt of the formula

    (C.sub.6 H.sub.5).sub.3.sup.⊕ P--CH.sub.2 CH═CH.sub.2 . HCO.sub.3.sup.63

was used as the phosphonium salt and the reaction product was analyzedin the same manner as Example 7. The results are set forth in Table 2.

                  TABLE 2                                                         ______________________________________                                                    Reaction time (hrs)                                                           1    1.5       2       3                                          ______________________________________                                        2,7-Octadien-1-ol                                                                           63.0   119.6     139.3 162.1                                    (mmoles)                                                                      1,7-Octadien-3-ol                                                                           4.0    7.6       8.9   10.4                                     (mmoles)                                                                      Total (mmoles)                                                                              67.0   127.2     148.2 172.5                                    ______________________________________                                    

EXAMPLES 9, 10 and 11

The reaction procedure of Example 7 was repeated except that 12 mmoleseach of the phosphonium salts mentioned in Table 3 were used as thephosphonium salts and the reaction products were analyzed as in Example7. The results are set forth in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Example   9              10                   11                              __________________________________________________________________________    Phosphonium salt                                                                         ##STR13##                                                                                    ##STR14##                                                                                          ##STR15##                      __________________________________________________________________________    Yield of NOD or                                                               IOD (mmoles)     NOD IOD         NOD IOD        NOD IOD                       __________________________________________________________________________    Reaction  1       63.3                                                                             4.2          58.5                                                                             3.0         60.7                                                                             3.1                       time      2      120.0                                                                             7.9         135.5                                                                             6.8        133.0                                                                             7.0                       (hrs)     3      139.5                                                                             9.1         150.3                                                                             8.0        155.3                                                                             8.3                       __________________________________________________________________________     (Note)                                                                        In the table, NOD stands for 2,7octadien-1-ol and IOD stands for              1,7octadien-3-ol.                                                        

EXAMPLE 12

The same reaction setup as used in Example 7 was charged with 60 g ofacetic acid, 101 g of triethylamine, 4.6 g (12.6 mmoles) of aphosphonium salt of the formula

    (C.sub.6 H.sub.5).sub.3.sup.⊕ P--CH.sub.2 CH═CH.sub.2 . HCO.sub.3.sup.⊖

and 0.43 g (0.42 mmole) of tris(dibenzylideneacetone)-palladium in anitrogen gas atmosphere, followed by addition of 50 ml of butadiene, andthe reaction was conducted at 75° C. for 3 hours. The contents were thenwithdrawn and analyzed by gas chromatography. The analysis revealed that1-acetoxy-2,7-octadiene and 3-acetoxy-1,7-octadiene had been produced inthe amounts of 352 mmoles and 60 mmoles, respectively.

EXAMPLE 13

The same reaction setup as used in Example 7 was charged with 50 g ofsulfolane, 50 g of methanol, 2.16 g (5 mmoles) of a phosphonium salt ofthe formula

    (C.sub.6 H.sub.5).sub.3.sup.⊕ P--CH.sub.2 CH═CHCH.sub.2 CH.sub.2 CH.sub.2 CH═CH.sub.2 . HCO.sub.3.sup.⊖

and 0.2 g (0.2 mmole) of tris(dibenzylideneacetone)-palladium in anitrogen gas atmosphere. Then, 20 g of butadiene was added and thereaction was conducted at 75° C. for 1.5 hours. After completion of thereaction, the reaction mixture was analyzed by gas chromatography. Theanalysis revealed that 1-methoxy-2,7-octadiene and3-methoxy-1,7-octadiene had been produced in the amounts of 17.7 g and4.7 g, respectively.

From the above reaction mixture, the product compounds were separated bydistillation at 75° C. in a vacuum of 25 mmHg using a film evaporator.The catalyst-containing sulfolane solution, obtained as a residue, wasstirred in an open system exposed to air at room temperature for 24hours. Analysis of the sulfolane solution after 24 hours of stirringrevealed no formation of phosphine oxide. To this sulfolane solutionwere added 50 g of methanol and 20 g of butadiene and the mixture wasreacted under the same conditions as in the first run. As a result, thereaction mixture contained 18.0 g of 1-methoxy-2,7-octadiene and 4.6 gof 3-methoxy-1,7-octadiene.

It is thus clear that the catalyst is highly stable against oxidationand still has high activity even after recovery from the reactionmixture.

EXAMPLE 14

The same reaction setup as used in Example 7 was charged with 67.8 mg(0.3 mmole) of palladium acetate, 6.2 g (12 mmoles) of a phosphoniumsalt of the formula ##STR16## 66 g of sulfolane, 68 g of water and 16.5g of triethylamine. Then, with the internal pressure being maintained at5 kg/cm² (gage pressure) using carbon dioxide gas, the temperature wasincreased to 60° C., and the mixture was stirred at 60° C. for 1 hour,after which the internal temperature was increased to 75° C. Then, 40 mlof butadiene was added in a single dose, whereupon the reaction startedinstantly. After 2 hours of reaction, the reaction mixture was analyzedby gas chromatography. The analysis revealed that 2,7-octadien-1-ol and1,7-octadien-3-ol had been produced in the amounts of 149 mmoles and 7.5mmoles, respectively.

EXAMPLE 15

The reaction procedure of Example 14 was repeated except that 12 mmolesof a phosphonium salt of the formula ##STR17## was used as thephosphonium salt and the reaction mixture was analyzed as in Example 14.As a result, the reaction mixture contained 153 mmoles of2,7-octadien-1-ol and 9.1 mmoles of 1,7-octadien-3-ol.

EXAMPLE 16

The same reaction setup as used in Example 7 was charged with 17.8 mg(0.1 mmole) of palladium chloride, 2.28 g (4.3 mmoles) of a phosphoniumsalt of the formula ##STR18## 5 mg (0.11 mmole) of formic acid, 25 ml oftriethylamine and 25 ml of acetic acid and the mixture was stirred in anitrogen gas atmosphere at room temperature for 30 minutes. Then, 20 mlof butadiene was added and the reaction was conducted at 75° C. for 3hours. As a result, 43 mmoles of 1-acetoxy-2,7-octadiene and 13 mmolesof 3-acetoxy-1,7-octadiene were produced.

COMPARATIVE EXAMPLE 1

The same reaction setup as used in Example 1 was charged with 70.0 g of95 wt.% aqueous solution of sulfolane, 63.0 g of ion exchanged water,16.5 g of triethylamine, 0.067 g of palladium acetate and 4.22 g oflithium diphenylphosphinobenzene-m-sulfonate, and carbon dioxide gas wasintroduced to establish a CO₂ partial pressure of 5 kg/cm² (gagepressure). The temperature was increased to 75° C. and 40 ml ofbutadiene was fed to initiate the reaction. After commencement of thereaction, the reaction mixture was sequentially analyzed by gaschromatography. As a result, an induction period of about 1 hour wasfound. After 3 hours of the reaction, the reaction mixture was analyzedby high performance liquid chromatography. The analysis showed a peak ofphosphine oxide ##STR19## at a retention time of 4.0 minutes. Results ofquantitative analysis of the products are given in Table 4.

                  TABLE 4                                                         ______________________________________                                                    Reaction time (hrs)                                                           1    1.5       2       3                                          ______________________________________                                        2,7-Octadien-1-ol                                                                           0      25.4      88.6  120.5                                    (mmoles)                                                                      1,7-Octadien-3-ol                                                                           0.2    8.8       10.0  12.1                                     (mmoles)                                                                      Total (mmoles)                                                                              0.2    34.2      98.6  132.6                                    ______________________________________                                    

COMPARATIVE EXAMPLE 2

The same reaction setup as used in Example 7 was charged with 100 g ofacetic acid, 20 g of triethylamine, 0.067 g of palladium acetate and 4.8g of sodium diphenylphosphinobenzene-m-sulfonate in a nitrogen gasatmosphere. Then, 50 ml of butadiene was fed and the reaction wasconducted at 75° C. for 3 hours. After 3 hours of reaction, the contentswere withdrawn and analyzed by gas chromatography. The analysis revealedsubstantially no production of 1-acetoxy-2,7-octadiene or3-acetoxy-1,7-octadiene. It is thus clear that the reaction rate is verylow when the concentration of the phosphine compound is high.

COMPARATIVE EXAMPLE 3

In 100 ml of sulfolane were dissolved 0.23 g oftetrakistriphenylphosphinepalladium and 1.31 g of triphenylphosphine.The resulting sulfolane solution was stirred at room temperature in anopen system exposed to air for 24 hours. As a result, 1.33 g ofphosphine oxide was formed and palladium metal separated out.

COMPARATIVE EXAMPLE 4

The reaction procedure of Example 14 was repeated except that 12 mmolesof a phosphonium salt of the formula ##STR20## was used as thephosphonium salt and the reaction mixture was analyzed as in Example 14.It was found that the reaction had not progressed at all.

EXAMPLE 17

In this example, a total of 30 runs were carried out using the reactorand extraction apparatus described below. Reactor: A 300-ml stainlesssteel autoclave equipped with a thermometer, stirrer, butadieneconstant-feed pump, carbon dioxide gas inlet, liquid feeding port andliquid drain port was used as the reactor. Extraction apparatus: A800-ml pressure-resistant glass autoclave equipped with a thermometer,stirrer, gas inlet, n-hexane feeding port and liquid pressure feedingport was used as the extraction apparatus. This extraction apparatus wasdirectly coupled to the above reactor. Method: The reactor was chargedwith 41 g of sulfolane, 45 g of distilled water, 14 g of triethylamine,0.2 mg [corresponding to a concentration of 2 mmoles/l-charged reactionmixture ] of trisdibenzylideneacetonepalladium, and 4.1 g of aphosphonium salt of the formula ##STR21## and after the internalatmosphere was sufficiently purged with carbon dioxide gas, the mixturewas heated to 70° C. with stirring and carbon dioxide gas was introducedto establish an internal pressure of 8 kg/cm² (gage pressure). Understirring at 600 r.p.m., 15 ml of liquid butadiene was fed and thereaction was conducted at 75° C. for 60 minutes with a furthercontinuous addition of butadiene at a rate of 14 ml/hr. The feeding ofbutadiene was stopped after 60 minutes of reaction and the reactionmixture was cooled and fed to the extraction apparatus by utilizing thepressure differential. After the extraction apparatus was pressurized to3 kg/cm² (gage pressure) with carbon dioxide gas, 100 ml of n-hexane wasadded at 20° C. After 15 minutes of stirring, the reaction mixture wasallowed to stand for 15 minutes for extraction with n-hexane. The upperlayer (n-hexane layer) was withdrawn from the system by utilizing thepressure differential. To the residue was added 100 ml of n-hexane forre-extraction and the upper layer was withdrawn from the extractionsystem. The n-hexane layers were combined and analyzed by gaschromatography for the reaction product and sulfolane, by Karl-Fischerdetermination for water, titrimetry for triethylamine, and atomicabsorption spectrometry and colorimetry for palladium and phosphorus(both on an atomic basis). The catalyst solution obtained as anextraction residue was supplemented with water in the amount equal tothe sum of that consumed in the reaction and that extracted into then-hexane layer, and triethylamine and sulfolane in the amounts equal tothose extracted into the n-hexane layer, respectively, and fed back tothe reactor by utilizing the pressure differential. Using the abovecatalyst solution, the series of reaction, extraction and catalystrecycling operations was repeated for a total of 30 runs. Throughoutthis series, no new addition of palladium and phosphorus components wasmade. The relation of the number of runs with reaction results and theamounts of palladium and phosphorus components extracted into then-hexane layer is shown in Table 5. It is clear from Table 5 that thecatalyst activity is maintained for a long time.

                  TABLE 5                                                         ______________________________________                                        Octadienol (Note 1)  Concentrations of                                                         NOD/IOD     catalyst components in                           Number  Yield    mole ratio  n-hexane layer (ppm)                             of runs (mmoles) (Note 2)    Pd     P                                         ______________________________________                                         5      71       95/5        0.6    0.07                                      10      71       95/5        0.6    0.06                                      15      70       95/5        0.5    0.06                                      20      70       95/5        0.5    0.05                                      25      70       95/5        0.5    0.05                                      30      70       95/5        0.5    0.05                                      ______________________________________                                         (Note 1) As products other than octadienols, 1,3,7octatriene and              dioctadienyl ether were detected and their yields were 1.2 to 1.3 mmoles      for the former and 0.4 to 0.6 mmoles for the latter.                          (Note 2) NOD stands for 2,7octadien-1-ol and IOD stands for                   1,7octadien-3-ol.                                                        

EXAMPLE 18

The same reaction setup as used in Example 5 was charged with 70.0 g of95 wt.% aqueous solution of sulfolane, 63.0 g of ion exchanged water,16.5 g of triethylamine, 2.7 g of allyl alcohol, 67.4 mg of palladiumacetate and 4.22 g of lithium diphenyl-phosphinobenzene-m-sulfonate andthe reaction was conducted in a carbon dioxide gas atmosphere at roomtemperature for 5 hours to prepare a catalyst solution. Analysis of thiscatalyst solution by high performance liquid chromatography showed nopeak of the starting material phosphine compound, indicating acompletion of transformation.

An autoclave equipped with an electromagnetic stirrer, carbon dioxidegas inlet, sampling line, feeding line and purging line was charged withthe whole amount of the above catalyst solution and carbon dioxide gaswas introduced to establish a carbon dioxide partial pressure of 5kg/cm² (gage pressure). Then, the temperature was set at 75° C. and 40ml of butadiene was fed for telomerization reaction. After commencementof the reaction, the reaction mixture was sequentially analyzed by gaschromatography for the reaction products 2,7-octadien-1-ol and1,7-octadien-3-ol. As a result, it was confirmed that the reaction hadprogressed without an induction period. Results of analysis by gaschromatography are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                                    Reaction time (hrs)                                                           1    1.5       2       3                                          ______________________________________                                        2,7-Octadien-1-ol                                                                           64.5   122.0     142.0 165.0                                    (mmoles)                                                                      1,7-Octadien-3-ol                                                                           3.2    6.5       7.5   8.7                                      (mmoles)                                                                      Total (mmoles)                                                                              67.7   128.5     149.5 173.7                                    ______________________________________                                    

Analysis of the catalyst solution by high performance liquidchromatography after 3 hours of reaction revealed no formation ofphosphine oxide.

EXAMPLE 19

The same reaction setup as used in Example 5 was charged with 70.0 g of95 wt.% aqueous solution of sulfolane, 20 g of ion exchanged water, 8.0g of 2,7-octadien-1-ol, 67.3 mg of palladium acetate and 3.7 g of sodium2-(diphenylphosphino)ethanesulfonate and the reaction was conducted in acarbon dioxide atmosphere at 50° C. for 10 hours to prepare a catalystsolution. Analysis of this catalyst solution by high performance liquidchromatography revealed no peak of the starting material phosphinecompound, indicating a completion of transformation.

The same reactor as used in Example 18 for telomerization reaction wascharged with 43 g of ion exchanged water and 16.5 g of triethylamine andcarbon dioxide was bubbled into the mixture. Then, the whole amount ofthe above catalyst solution was fed and in the same manner as Example18, the telomerization reaction was conducted and the reaction mixturewas sequentially analyzed by gas chromatography. As a result, it wasconfirmed that the reaction had proceeded without an induction period.Results of gas chromatographic analysis are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                    Reaction time (hrs)                                                           1    1.5       2       3                                          ______________________________________                                        2,7-Octadien-1-ol                                                                           48.2   94.8      115.5 146.9                                    (mmoles)                                                                      1,7-Octadien-3-ol                                                                           5.6    8.6       9.8   11.5                                     (mmoles)                                                                      Total (mmoles)                                                                              53.8   103.4     125.3 158.4                                    ______________________________________                                    

Analysis of the catalyst solution by high performance chromatographyafter 3 hours of reaction revealed no formation of phosphine oxide.

EXAMPLE 20

A 50-milliliter three-necked flask was charged with 20 g of 95 wt.%aqueous solution of sulfolane, 5 g of ion exchanged water, 0.067 g ofpalladium acetate, 4.8 g of sodium diphenylphosphinobenzene-m-sulfonateand 1.4 g of allyl alcohol and while carbon dioxide gas was bubbled intothe mixture, the reaction mixture was stirred at 50° C. for 4 hours.Analysis of the resulting catalyst solution by high performance liquidchromatography revealed no peak of the starting material phosphinecompound, indicating a completion of transformation.

The same reaction setup as used for telomerization reaction in Example18 was charged with 100 g of acetic acid, 20 g of triethylamine and thewhole amount of the above catalyst solution in a nitrogen gasatmosphere. Then, 30 ml of butadiene was fed and the reaction wasconducted at 80° C. for 3 hours. After 3 hours of reaction, the contentswere withdrawn and analyzed by gas chromatography. The analysis revealedthe formation of 1-acetoxy-2,7-octadiene and 3-acetoxy-1,7-octadiene inthe yields of 52 mmoles and 15 mmoles, respectively. Analysis of thecatalyst solution by high performance liquid chromatography after 3hours of reaction showed no formation of phosphine oxide at all.

EXAMPLE 21

The same reaction setup as used in Example 7 was charged with 50 g ofsulfolane, 0.2 g of 1-acetoxy-2,7-octadiene, 28 mg of palladium acetateand 0.17 g of di(n-butyl)phenylphosphine. The reaction was conducted at50° C. for 2 hours to prepare a catalyst solution. Analysis of thecatalyst solution by high performance liquid chromatography revealed nopeak of the starting material phosphine compound, indicating acompletion of transformation.

To the catalyst solution in the reaction setup were added 26 g of formicacid and 57 g of triethylamine and the mixture was stirred for 15minutes. Then, 60 g of butadiene was added and the reaction wasconducted at 70° C. for 2 hours. Analysis of the reaction mixture after2 hours of reaction showed the formation of 48 g of 1,7-octadiene and7.2 g of 1,6-octadiene.

What is claimed is:
 1. A process for producing a straight-chain alkadienyl compound which comprises reacting a conjugated diene with an active hydrogen compound in the presence of a telomerization catalyst, characterized in that a catalyst comprising a phosphonium salt of the general formula ##STR22## wherein R¹ and R² each is a hydrogen atom or a hydrocarbon group of 1 to 12 carbon atoms which may optionally be substituted; R³ is a hydrogen atom or a hydrocarbon group 1 to 5 carbon atoms which may optionally be substituted; R⁴, R⁵ and R⁶ each is a hydrocarbon group of 1 to 8 carbon atoms which may be substituted, at least one of R⁴, R⁵ and R⁶ being an aryl group; X is a hydroxyl group, a hydroxycarbonyloxy group or a lower alkylcarbonyloxy group and a palladium compound is used as said telomerization catalyst, the substituents of the substituted hydrocarbons being di(lower alkyl)amino, cyano, --SO₃ M or --COOM, wherein M is an alkali metal.
 2. The process claimed in claim 1 wherein the phosphonium salt of general formula (I) wherein R¹ and R² each is a hydrogen atom or an aliphatic hydrocarbon group of 1 to 12 carbon atoms and R³ is a hydrogen atom or an aliphatic hydrocarbon group of 1 to 5 carbon atoms is used.
 3. The process claimed in claim 1 wherein the phosphonium salt of general formula (I) wherein R⁴, R⁵ and R⁶ each is an aryl group of 6 to 8 carbon atoms which may optionally be substituted by a group of the formula --SO₃ M (where M is an alkali metal atom) is used.
 4. The process claimed in claim 1 wherein the proportion of said phosphonium salt in the catalyst is at least 6 moles per gram-atom of palladium in said palladium compound.
 5. The process claimed in claim 4 wherein the proportion of said phosphonium salt in the catalyst is in the range of 10 to 200 moles per gram-atom of palladium in said palladium compound. 